Multicomponent compositions for mercury removal

ABSTRACT

Herein are disclosed compositions of matter, processes of manufacture and processes of use of solid state admixtures that include an inorganic base and a sulfide selected from the group consisting of an ammonium sulfide, an alkali metal sulfide, an alkali-earth metal sulfide, transition metal sulfide, and a mixture thereof. The composition can include solid state inorganic bases (e.g., calcium hydroxide and sodium sesquicarbonate) and/or gaseous bases (e.g., ammonia) and, optionally, a support material for one or more of the inorganic base and sulfide. The compositions are useful for capturing environmental contaminants, for example, from the flue gas of a coal fired power plant.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.14/774,254, filed Sep. 10, 2015, entitled “Multicomponent Compositionsfor Mercury Removal,” which is a national stage application under 35U.S.C. § 371 of International Application No. PCT/US2014/023989, filedMar. 12, 2014, entitled “Multicomponent Compositions for MercuryRemoval,” which claims priority to U.S. Provisional Patent ApplicationNo. 61/778,778, filed Mar. 13, 2013, the contents of all of which arehereby incorporated herein in their entirety by reference for allpurposes.

FIELD OF THE INVENTION

The present invention is directed to methods of using compositions forremoving one or more environmental contaminant(s) (e.g., mercury orsulfur) from gas streams, e.g., industrial smoke stacks; flue ducts, andthe like. The compositions, “flue gas scrubbing compositions”, areparticularly useful for removal of mercury from the flue gas emitted bycoal-burning electrical power plants.

BACKGROUND

Environmental contaminants contained in emissions from coal-fired andoil-fired power plants are a major environmental concern. Particulatematter (e.g., fly ash), nitrates, sulfates, and mercury emissions arerestricted because these emissions can yield, for example, acid rain andserious neurotoxic effects. The removal of particulate matter has beenaddressed through the installation of baghouses, electrostaticprecipitators, cyclone separators, or cyclone separators with baghousefilters in the flue gas ducts. The removal of nitrates and sulfates hasbeen addressed through the addition of lime (calcium oxides and/orhydroxides) to the flue gas and the collection of the lime reactionproduct (e.g., CaSO₄) with the particulate matter. The removal ofmercury can be addressed by absorption with a mercury absorbentmaterial. Unfortunately, the mercury absorbent materials and lime areoften chemically incompatible and/or the mercury absorbent material isfiscally incompatible with the collection and disposal of theparticulate material which is often sold into the concrete industry.

The most common method for reduction of mercury emissions fromcoal-fired and oil-fired power plants is the injection of powdered,activated carbon into the flue gas stream. The activated carbon is ahigh surface area material that provides for the adsorption of themercury and the agglomeration of the particle bound mercury. Thedisadvantage of adding activated carbon into the flue gas stream is theretention of the activated carbon in the fly ash waste stream. Fly ashfrom coal-fired power plants is often added to concrete, where thepresence of the activated carbon adversely affects performance, therebymaking the inclusion of the carbon fiscally incompatible with the fluegas scrubbing process.

Another method for reducing Hg emissions is through the addition ofchemical species that react with mercury to chem-adsorb the elementaland oxidized mercury. One class of materials capable of chemicallyreacting with Hg is metal sulfides. U.S. Pat. Nos. 6,719,828 and7,578,869 teach the preparation of supported metal sulfides. A majordisadvantage of these supported metal sulfides is that these materialsare known to react with lime, for example, yielding copper metal andcalcium sulfide materials. See e.g., Habashi et al., MetallurgicalTransactions, 1973, 4, 1865. These reaction products destroy theabsorptive capacity of mercury from the flue gas. Therefore, the use ofsupported metal sulfides has been physically separated from the use oflime in the flue gas scrubbing process.

There is still an ongoing need to provide improved pollution controlsorbents and methods of their manufacture, particularly sorbents thatare stable both in acidic flue gases and in the presence of acidreducing species.

SUMMARY

One embodiment is a composition that includes a solid state admixture ofan inorganic base and a sulfide selected from the group consisting of anammonium sulfide, an alkali metal sulfide, an alkali-earth metalsulfide, transition metal sulfide, and a mixture thereof.

Another embodiment is a manufacturing process that includes providingthe solid state admixture by intimately mixing the inorganic base andthe sulfide.

Still another embodiment is a process of capturing an environmentalcontaminant from a fluid, the process that includes admixing a fluidcontaining an environmental contaminant with the composition thatincludes the solid state admixture; and separating the fluid and thecomposition; wherein the separated fluid includes a lower concentrationof the environmental contaminant after separation from the composition.

Yet another embodiment is a composition that includes an admixture ofanhydrous ammonia and a supported sulfide, the supported sulfidecomprising a sulfide selected from the group consisting of an alkalimetal sulfide, an alkali-earth metal sulfide, transition metal sulfide,and a mixture thereof, and a support selected from the group consistingof a silicate, an aluminate, an aluminosilicate, a carbon, and a mixturethereof.

Still yet another embodiment is a process of capturing an environmentalcontaminant from a fluid, the process includes admixing a fluidcontaining an environmental contaminant with anhydrous ammonia; admixingthe fluid containing the environmental contaminant with a supportedsulfide; and admixing the anhydrous ammonia and the supported sulfide inthe fluid; wherein the supported sulfide comprises a sulfide selectedfrom the group consisting of an alkali metal sulfide, an alkali-earthmetal sulfide, transition metal sulfide, and a mixture thereof, and asupport selected from the group consisting of a silicate, an aluminate,an aluminosilicate, a carbon, and a mixture thereof.

Another embodiment is a process of capturing an environmentalcontaminant from a fluid, the process includes admixing anhydrousammonia and a supported sulfide to provide a composition; and admixingthe composition with the fluid containing an environmental contaminant;wherein the supported sulfide comprises a sulfide selected from thegroup consisting of an alkali metal sulfide, an alkali-earth metalsulfide, transition metal sulfide, and a mixture thereof, and a supportselected from the group consisting of a silicate, an aluminate, analuminosilicate, a carbon, and a mixture thereof.

DETAILED DESCRIPTION

A first embodiment is a composition that includes a solid stateadmixture of an inorganic base and a sulfide selected from the groupconsisting of an ammonium sulfide, an alkali metal sulfide, analkali-earth metal sulfide, transition metal sulfide, and a mixturethereof. In one preferable example, the composition includes a supportcarrying the admixture. Preferably, the support is selected from thegroup consisting of a silicate, an aluminate, an aluminosilicate, acarbon, and a mixture thereof. For example, the support can be aphyllosilicate selected from the group consisting of bentonite,montmorillonite, hectorite, beidellite, saponite, nontronite,volkonskoite, sauconite, stevensite, fluorohectorite, laponite,rectonite, vermiculite, illite, a micaceous mineral, makatite, kanemite,octasilicate (illierite), magadiite, kenyaite, attapulgite,palygorskite, sepoilite, and a mixture thereof. The support can be asmectite clay e.g., bentonite, montmorillonite, hectorite, beidellite,saponite, nontronite, volkonskoite, sauconite, stevensite, and/or asynthetic smectite derivative, particularly fluorohectorite andlaponite; a mixed layered clay, particularly rectonite and theirsynthetic derivatives; vermiculite, illite, micaceous minerals, andtheir synthetic derivatives; layered hydrated crystalline polysilicates,particularly makatite, kanemite, octasilicate (illierite), magadiiteand/or kenyaite; attapulgite, palygorskite, sepoilite; or anycombination thereof. The support can be an activated carbon, a powderactivated carbon, a graphite, or a mixture thereof. More preferably, theadmixture is distributed on the surface of the support.

In a preferred example, the support carries the admixture. Herein thismeans the support is in intimate contact with each individual componentof the admixture (e.g., the inorganic base and, individually, thesulfide). In one instance, a portion of the inorganic base and a portionof the sulfide are supported on a support particulate. That is, thesupport is preferable a particulate material (e.g., consists of aplurality of distinct particles) and, in this instance, a singleparticulate carries both the inorganic base and the sulfide. Notably,the inorganic base and/or the sulfide can be particulates, preferably,having a particle diameter less than 25%, 20%, 15%, or 10% of a particlediameter of the support. In another instance, the inorganic base and thesulfide can be carried on distinct supports. For example, a plurality ofparticles of the support can carry the inorganic base and a plurality ofparticles of the support can carry the sulfide. In a subset of thisinstance, the support carrying the inorganic based is distinct from thesupport carrying the sulfide, the distinction can be in particle size,composition, or a combination thereof. Still further, the compositioncan include an admixture of a plurality of particles where two areselected from the group consisting of the support carrying the inorganicbase, the support carrying the sulfide, and the support carrying boththe inorganic based and the sulfide.

The solid state admixture of an inorganic base and a sulfide can includedistinct phases, regions or particulates of each of the inorganic baseand sulfide and/or can include the reaction product of the inorganicbase and the sulfide. In a preferable instance, the admixture includesdistinct phases, regions or particulates (e.g., crystallites) of theinorganic base and the sulfide. In instances wherein the admixtureconsist of or consist essentially of distinct phases, regions orparticulates of the inorganic base and sulfide, the inorganic base cancarry the sulfide and/or the sulfide can carry the inorganic base.Examples include core-shell arrangements and agglomerations of smallerparticulates upon a larger particulate.

In one instance, the inorganic base can be selected from the groupconsisting of calcium hydroxide, sodium sesquicarbonate (trisodiumhydrogendicarbonate), sodium carbonate, sodium bicarbonate, potassiumcarbonate, calcium carbonate, and a mixture thereof. Preferably, theinorganic base is selected from calcium hydroxide and sodiumsesquicarbonate. In one example, the inorganic base is calcium hydroxide(e.g., hydrated lime); in another example, the inorganic base is sodiumsesquicarbonate (e.g., trona).

The calcium hydroxide can be hydrated lime; hydrated lime is a drypowder manufactured by treating quicklime with sufficient water tosatisfy its chemical affinity for water, thereby converting the oxidesto hydroxides. Depending upon the type of quicklime used and thehydrating conditions employed, the amount of water in chemicalcombination varies, for example: high calcium hydrated lime containsgenerally 72% to 74% calcium oxide and 23% to 24% chemically combinedwater; dolomitic hydrated lime (normal) contains about 46% to 48%calcium oxide, 33% to 34% magnesium oxide, and 15% to 17% chemicallycombined water; dolomitic hydrated lime (pressure) contains about 40% to42% calcium oxide, 29% to 30% magnesium oxide, and 25% to 27% chemicallycombined water.

The sulfide can be a terminal or bridged sulfide (i.e., S²⁻); can be apolysulfide (e.g., S₂ ²⁻, S₃ ²⁻, S₄ ²⁻, S_(n) ²⁻); can be a thiolate(i.e., SH⁻, SR⁻); or can be a hydropolysulfide (e.g., S₂H⁻). In oneexample, the sulfide is a polysulfide. In an example, the sulfide can bea transition metal sulfide selected from the group consisting of amanganese sulfide, an iron sulfide, a cobalt sulfide, a nickel sulfide,a copper sulfide, a zinc sulfide, and alloy thereof, and a mixturethereof.

In another instance, the composition can be described as a sulfidemodified support carrying the inorganic base. For example, thecomposition include a support modified with a transition metal sulfide(e.g., manganese sulfide, iron sulfide, cobalt sulfide, nickel sulfide,copper sulfide, zinc sulfide, alloys thereof, and mixture thereof) wherethe modified support carries the inorganic base (e.g., trona and/orcalcium hydroxide).

In one specific example, the inorganic base is a calcium hydroxide, thesulfide is a copper sulfide and the support is selected from the groupconsisting of bentonite and montmorillonite. In another specificexample, the inorganic base is a calcium hydroxide, the sulfide is analkali metal sulfide and the support is selected from the groupconsisting of bentonite and montmorillonite. In yet another specificexample, the inorganic base is sodium sesquicarbonate, the sulfide is acopper sulfide and the support is selected from the group consisting ofbentonite and montmorillonite. In still another specific example, theinorganic base is sodium sesquicarbonate, the sulfide is an alkali metalsulfide and the support is selected from the group consisting ofbentonite and montmorillonite.

Another embodiment is a process for manufacturing the above describedcompositions. The process can include providing the solid stateadmixture by intimately mixing the inorganic base and the sulfide. Theintimate mixing can be provided by a process selected from the groupconsisting of ball milling, extruding, solid state mixing, grinding,coprecipitation, and a mixture thereof. The intimate mixing, preferably,includes reducing particle diameters of the inorganic base in thepresence of the sulfide and/or reducing particle diameters of thesulfide in the presence of the inorganic base. Preferably, the processincludes intimately mixing the inorganic base and the sulfide with asupport; and when the support is included, the intimately mixingincludes reducing the particle diameter of the support.

Still another embodiment is a process of capturing an environmentalcontaminant from a fluid employing the above described compositions. Theprocess can include admixing a fluid containing an environmentalcontaminant with the above described composition, and then separatingthe fluid and the composition. The separated fluid preferably includes alower concentration of the environmental contaminant after separationfrom the composition. Notably, the fluid can be a liquid or a gas. Inone example the fluid is the flue gas produced by the combustion ofcoal. In another example, the fluid is a wet scrubber's dischargeliquor.

The environmental contaminant can be mercury, selenium, lead, chromium,arsenic, cadmium, and a mixture thereof. Preferably, the describedcompositions separate mercury from the fluid.

In still yet another embodiment, a composition can include an admixtureof anhydrous ammonia and a supported sulfide. The supported sulfideincludes at least a sulfide selected from the group consisting of analkali metal sulfide, an alkali-earth metal sulfide, transition metalsulfide, and a mixture thereof, and a support selected from the groupconsisting of a silicate, an aluminate, an aluminosilicate, a carbon,and a mixture thereof. In one example, the admixture includes ammoniumcations formed by a reaction of the anhydrous ammonia with the support.In another example, the admixture includes ammonia adhered to thesurface of the supported sulfide.

In yet another embodiment, a process of capturing an environmentalcontaminant from a fluid can include admixing a fluid containing anenvironmental contaminant with anhydrous ammonia; admixing the fluidcontaining the environmental contaminant with a supported sulfide; andadmixing the anhydrous ammonia and the supported sulfide in the fluid.The supported sulfide includes at least a sulfide selected from thegroup consisting of an alkali metal sulfide, an alkali-earth metalsulfide, transition metal sulfide, and a mixture thereof, and a supportselected from the group consisting of a silicate, an aluminate, analuminosilicate, a carbon, and a mixture thereof.

In still another embodiment, a process of capturing an environmentalcontaminant from a fluid can include admixing anhydrous ammonia and asupported sulfide to provide a composition; and admixing the compositionwith the fluid containing an environmental contaminant. The supportedsulfide includes at least a sulfide selected from the group consistingof an alkali metal sulfide, an alkali-earth metal sulfide, transitionmetal sulfide, and a mixture thereof, and a support selected from thegroup consisting of a silicate, an aluminate, an aluminosilicate, acarbon, and a mixture thereof.

The foregoing description is given for clearness of understanding only,and no unnecessary limitations should be understood therefrom, asmodifications within the scope of the invention may be apparent to thosehaving ordinary skill in the art.

What is claimed:
 1. A composition comprising: a solid state admixture ofan inorganic base and a sulfide selected from the group consisting of anammonium sulfide, an alkali metal sulfide, an alkali-earth metalsulfide, transition metal sulfide, and a mixture thereof.
 2. Thecomposition of claim 1 consisting essentially of an admixture of theinorganic base and the sulfide.
 3. The composition of claim 1 furthercomprising a support carrying the admixture.
 4. The composition of claim3, wherein the composition consists essentially of the support carryingthe admixture.
 5. The composition of claims 3-4, wherein the support isselected from the group consisting of a silicate, an aluminate, analuminosilicate, a carbon, and a mixture thereof.
 6. The composition ofany one of claims 3-5, wherein the support is a phyllosilicate selectedfrom the group consisting of bentonite, montmorillonite, hectorite,beidellite, saponite, nontronite, volkonskoite, sauconite, stevensite,fluorohectorite, laponite, rectonite, vermiculite, illite, a micaceousmineral, makatite, kanemite, octasilicate (illierite), magadiite,kenyaite, attapulgite, palygorskite, sepoilite, and a mixture thereof.7. The composition of any one of the preceding claims, wherein theinorganic base is selected from the group consisting of calciumhydroxide, sodium sesquicarbonate (trisodium hydrogendicarbonate),sodium carbonate, sodium bicarbonate, potassium carbonate, calciumcarbonate, and a mixture thereof.
 8. The composition of claim 7, whereinthe inorganic base is selected from the group consisting of calciumhydroxide, sodium sesquicarbonate, and a mixture thereof.
 9. Thecomposition of any one of the preceding claims, wherein the sulfide is apolysulfide.
 10. The composition of any one of the preceding claims,wherein the sulfide is a transition metal sulfide selected from thegroup consisting of a manganese sulfide, an iron sulfide, a cobaltsulfide, a nickel sulfide, a copper sulfide, a zinc sulfide, and amixture thereof.
 11. The composition of any one of claims 3-10, whereinthe inorganic base is a calcium hydroxide, the sulfide is a coppersulfide and the support is selected from the group consisting ofbentonite and montmorillonite.
 12. The composition of any one of claims3-10, wherein the inorganic base is a calcium hydroxide, the sulfide isan alkali metal sulfide and the support is selected from the groupconsisting of bentonite and montmorillonite.
 13. The composition of anyone of claims 3-10, wherein the inorganic base is sodiumsesquicarbonate, the sulfide is a copper sulfide and the support isselected from the group consisting of bentonite and montmorillonite. 14.The composition of any one of claims 3-10, wherein the inorganic base issodium sesquicarbonate, the sulfide is an alkali metal sulfide and thesupport is selected from the group consisting of bentonite andmontmorillonite.
 15. The composition of any one of claim 3-14, whereinthe admixture is distributed on the surface of the support.
 16. Theprocess of capturing an environmental contaminant from a fluid, theprocess comprising: admixing a fluid containing an environmentalcontaminant with the composition of any one of claim 1-15; andseparating the fluid and the composition; wherein the separated fluidincludes a lower concentration of the environmental contaminant afterseparation from the composition.